JPS5998002A - Liquid agricultural drug composition in form of suspension concentrate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to liquid formulations of pesticides in the form of suspension concentrates.

Generally, pesticide substances are applied in the form of emulsions, wettable powders or suspension concentrates. Active substances that are poorly soluble in technical grade solvents are generally applied in the form of water conservers. However, the manufacture of these formulations requires expensive grinding and filtration equipment and expensive and often expensive carriers. Furthermore, irrigation agents have the disadvantage of generating dust when handled, making their dosing difficult. There is a risk of contamination and damage to the health of the user with such powdered preparations. Spray liquids prepared from irrigation agents tend to be non-uniform as the particles of active substances and solids settle out relatively quickly.

Unlike irrigation agents, aqueous suspensions 1 do not have these flash points. Its production does not require a filtering device, so
Equipment costs are relatively low.

However, it is difficult to develop suspension concentrates that are storage stable and suitable for practical applications. Emulsions and wettable powders are single-phase systems, whereas aqueous suspension concentrates of solid active substances are two-phase systems (solid/liquid), which are generally unstable and tend to separate. This tendency increases as the storage time increases and the storage temperature increases. However, for practical purposes, the suspension concentrate must be storage stable for more than two years and must also remain fluid.

That is, solidification of the suspension and/or formation of irreversible precipitates must be avoided.

Although theories exist regarding the conditions that will form a stable suspension, it is not possible to predict directly the optimal formulation additive due to the large number of criteria that must be considered. .

Thus, for example, testing the suspension properties of a single production batch is not practically sufficient. This is because even small changes in the proportions of secondary components in individual batches of active substance can have a decisive negative effect on the stability of the dispersion.

Numerous compositions of suspension concentrates are known from the literature. Known pesticides, such as active substances such as triphenyltin compounds, ureas such as diuron or linuron, triazines such as simazine and atrazine, are disclosed in US Pat. No. 4.07.
1. Optimal formulations are not obtained when formulated with partially hydrolyzed polyvinyl acetate as described in S 17 specification 1'. This is because these formulation aids lead to the formation of viscous precipitates that cannot be redispersed. Similar results have been obtained, for example, in US Pat. No. 6.948.636 or British Patent No. 1.480.
．． It is also observed when using non-ionic emulsifiers, vegetable gums and anionic surfactants for formulation according to No. 110.

Nonionic emulsifiers containing polyglycolethers often cause crystal formation, for example in the case of diuron, a relatively sparingly soluble pesticide. The use of high-molecular polydarycol ethers in addition to the dispersing agent, even when silicic acid is added (German Patent Application No. 2.547)
．． 968 and 2.651.046), a dispersion is obtained in which an irreversible precipitate settles out during storage. When pesticides are formulated using polycarboxylated vinyl polymers, such as polymethacrylates (U.S. Patent No. 3.
060.084), viscous precipitates also often form during storage.

Furthermore, when formulating such pesticides with polycarboxylated vinyl polymers according to German Patent Application No. 2.651.046, they thicken or form a viscous precipitate at 40-50°C. This results in a liquid suspension concentrate which is therefore unsuitable for use and quite stable for storage.

Dispersions containing lignin sulfonate as a formulation agent according to US Pat. No. 3,157,486 and ethyl polyglycol ether together with the sodium salt of the condensation product of sulfonated phenol and formaldehyde according to European Patent No. 22,925. Dispersions containing alkali metal salts of phosphate esters have poor storage stability in the case of the active substances mentioned. Furthermore, suspension concentrates obtained using the above-mentioned formulation aids often do not have sufficient millability in ball mills, which is necessary for their production.

This is especially true in the case of formulations whose viscosity is highly dependent on temperature, so that these suspensions d:
, which occurs during the grinding process, often becomes viscous at temperatures of 55°C.

The present inventors have now discovered that a surprisingly large number of pesticides such as insecticides, insecticides, acaricides, herbicides and fungicides (Cl1, as formulation aids, from sodium sulfite, maleic anhydride and alkylphenol polyglycol ethers) The storage stability was increased by using the prepared sulfoconolyl ester with a mixture of equal parts of a salt of lignin sulfonic acid and a swellable alkaline earth metal silica salt. The scales and all found are formulated as liquid suspension concentrates.

The object of the invention is therefore to coat a liquid agrochemical composition in the form of an aqueous suspension concentrate, in addition to the active substance mixture t(r), containing (Os - Cl2) - A sulfoconopropyl ether prepared by reacting a polyglycol ether of the condensation product of alkylphenol and formaldehyde with maleic anhydride and an alkali metal sulfite.
The liquid agrochemical composition is characterized in that it contains an alkali metal salt of a lignin sulfonic acid half-ester and an alkali metal salt of lignin sulfonic acid mixed with equidistant portions of a swellable alkaline earth metal silicate. Certain 9 alkali metal salts of sulfocono half esters to be used according to the invention are prepared according to German Patent No. 2.132.4 Q 5, in particular monooctylphenol or monononylphenol being used and alkylphenols :Formaldehyde molar ratio varies between 2:1 and 10:9. The polyglycol ether of the condensation product of arnalphenol and formaldehyde preferably contains from 2 to 8 moles of alkylene oxide units, especially ethylene oxide units, per mole of alkylphenol. As alkali metal sulfite, preferably sodium sulfite is used.

Refers to the alkali metal salts of sulfosuccinic acid half esters, especially the sodium salts.

A preferred sulfocono-20 half ester is prepared from, for example, 3 moles of nonylphenol, 18 moles of ethylene oxide, 2 moles of formaldehyde, 3 moles of sodium sulfite and 3 moles of maleic anhydride, and is prepared as a dry powder or in an aqueous solution (generally 35 moles of used in the form of fire).

As the alkali metal salt of ligninsulfonic acid, sodium salt is mainly used. Suitable swellable alkaline earth metal silicates are, in particular, silicic acids (magnesium silicates) and preferably the mineral montmorillonite. Vanderbilt Corporation (on
') Registered trademark name ■Durban (Darvan)
It is commercially available as Na3.

Suitable active substances a=t of the agrochemical composition according to the invention
, insecticides such as endosulfan, triphenyltin compounds, especially fentin hydroxide, as well as fungicides such as carbengzim, mancozep, monolinuron, monolon, isofuroturon, chlortoluron, especially Diuron No. 2 Chlortoruron as well as mixtures thereof are further added to the composition according to the invention.
! The usual formulation auxiliaries of g11 can be used.
．． (σr1 Normal humidity (consolidation and dispersing agents, e.g. polyoxyethylated alkylphenols\polyoxyepulated fatty alcohols, tridecyl alcohol polylicol ether (Genapo), X-080),
alkyl- or alkylphenyl sulfone), sodium lidanitsulfonate, sodium 2,2'-cinna7tylmethane-6,6'-disulfonate, sodium diptylnaphthalenesulfonate 1) Rum or sodium oleylmethyltaurate, swelling agent , for example swellable aluminosilicates (C1: swellable polysaccharides, e.g. Kelsan (■
xanthomas (Xantho) such as
mas) produced by fermentation of carbohydrates using microorganisms can be used. Furthermore, as formulation auxiliaries silicone antifoaming agents such as tributyl phosphate or dialkylpolinosiloxanes, as well as ethylene glycol, phlopylene gellicol, glycerin,
Other antifreeze agents, especially ethylene glycol, emollients such as urea and customary preservatives such as benzoic acid, lupitanic acid, formaldehyde, trace amounts of bactericidal substances, etc. may be added.

The vessel for producing the suspension concentrate according to the invention contains ordinary tap water, process water or deionized water, preferably 20
Water with a hardness of °dH (German hardness) can be used.

The composition of the invention contains 5-60% by weight of active substance, 'l'4
i1/1c15-50mff1%, alkali metal salt of sulfosuccinic acid half ester 0.5-30% by weight, preferably 2-20% by weight, combination of alkali metal salt of lignin sulfonic acid and swellable alkaline earth metal silicate The mixture of equidistant parts may contain 0.5 to 4% by weight. As a formulation aid,
Additionally, 0-0.2% by weight of swellable polysaccharides, 0-3.0% by weight of conventional wetting or dispersing agents, 0-10% by weight of antifreeze agents,
0 to 8% by weight of a softening agent, 0 to 2% by weight of a preservative and 0 to 3% by weight of an antifoaming agent may be added. The balance of up to 100 weight rings of the composition of the invention consists of water.

Suspension concentrates according to the invention are liquid and easily flowable. : Width<Preferably, their viscosity is 69℃
It will not increase even if the temperature rises to . This viscosity may even be reduced without adversely affecting the suspension and dilutability of these concentrates in water. This is important for temporary storage and application in regions with hot climates. The products constructed according to the invention can be easily ground, they have very good wettability and good dilutability with the addition of water. They are furthermore very compatible when formulated with combination active substances, which are often applied to widen the range of biological action.

On the other hand, if only one of the three formulation components according to the invention is missing, namely sulfosuccinic acid half ester, lignin sulfonate and swellable alkaline earth metal silicate, the 3, according to the invention, The advantageous properties of the component combination, in particular storage stability, flowability and viscosity properties at elevated storage temperatures, are completely lost. Similarly, an advantageous property of the compositions according to the invention is that when the composition of the sulfosuccinic acid half ester is modified by the omission or addition of one component, e.g.
It will also be lost if it does not contain nocol ether components.

In order to produce a suspension concentrate according to the invention, it is possible, for example, to stir the active substance or active substance mixture in an aqueous solution or suspension of the formulation aid and to obtain a coarse The suspension of particles is optionally ground to a fineness of about 200 microns in a frundum tisfum mill or toothed disc mill, and the product is then ground to a fineness of about 200 microns, with particles of the suspension ranging from 0.1 to 10 microns. The Pearl Mill/ζ is milled in a Sunto Mill, preferably to a particle size of less than 5 microns. Particle size is determined by Tisf centrifuge or Coulter counter equipment.

The use of the composition according to the invention is carried out in a simple manner by diluting the suspension ml condensate with the desired amount of water, stirring briefly and applying to the plants. From the suspension concentrate according to the invention? Compared to those prepared from wettable powders or emulsions, the four-layer spray solutions are superior, in particular, to the homogeneous distribution of the active substance, which is retained even after standing for 24 hours. In contrast, suspensions of irrigation agents separate very quickly and often only 1/2
After standing for a while, it will already settle to the bottom and be shaken off. Similarly,
After the emulsion is allowed to stand for 1 to 4 hours, the emulsified concentrate precipitates and becomes oily or creamy.

Furthermore, the suspension concentrate according to the invention can surprisingly contain the known herbicides, insecticides and the like, which in the case of right tin liquids can be added in the form of an aqueous solution or an emulsion. It has excellent physical compatibility with fungicides.

The following examples illustrate the invention in further detail.

Examples 1 to 17 A free-flowing suspension of the following active substances having the following composition is prepared by milling the respective ingredients in a pearl mill filled with glass spheres with a diameter of 2 dishes (see section 1 below). (See Table 1).

The dispersion is milled to a fineness such that 90% by weight of the suspended particles have a diameter of 5 microns or less and 30-40% by weight of the particles have a diameter of 1 micron or less. The particle size is then determined by disk centrifugation.

When each 2 ml portion of the suspension concentrate so obtained was poured into water 99rnA, dilution of the suspension occurred spontaneously and no sedimentation occurred even after standing for 12 hours. Only traces of particles are visible. Unlike in the case of Hykkei and Shiuru Hydrostatic 1 agents, the suspendability is almost 100% in these cases (measured according to the 'CI PAC test standard).

The resulting dispersion is easily pourable and remains stable even after 3 months of storage with storage temperature variations from -]O<0>C to +50<0>C.

No sediment formation is observed. Sometimes only a portion (5-10% by volume) of the carrier liquid separates, but by shaking twice this portion is naturally remixed with the other ingredients. No crystal growth of the active substance particles is observed in any case.

The viscosity of the dispersion generally increases with increasing storage temperature, but on the contrary its fluidity increases without adversely affecting its stability.

/ / Comparative Example ■ Example 2.5. for preparing a dispersion of the active substances of Table 1.
(operating according to 3, 9, 12 and 13, except that dispersant 1 is a sulfo group-containing condensation product of alkylphenol and formaldehyde, e.g. omitting the polyglycol ether component), the resulting suspension concentrate teeth,
Already after one month of storage at 00 DEG C., it becomes unstable and a jelly-like to viscous partially solid precipitate forms which cannot be redispersed. These dispersions can no longer be used.

Comparative Example■ Example 1, 2.5゜6.
9.12 and 13, except that dispersant 2 is a sodium salt of naphthalene sulfonic acid condensed with formaldehyde, such as tamol NN0 ((R)
Similar results are observed when other known dispersants are used in place of the condensation product of naphthalene sulfonic acid in the case of substitution with only the sthorium salt of polygenin sulfonic acid (I'amol NNQ) . These dispersions can also no longer be used.

Claims (1)

[Claims] 1. In a liquid agrochemical composition in the form of an aqueous suspension concentrate, in addition to the active substance or active substance mixture, ((!8
Alkali metal salts of sulfonic acid half esters prepared by reacting polyglycol ethers of condensation products of C12')-alkylphenols and formaldehyde with maleic anhydride and alkali metal sulfites, and swellable alkali Liquid agrochemical composition as described above, characterized in that it contains an alkali metal salt of ligninsulfonic acid mixed with an equivalent part of an earth metal silicate. 2. The polyglycol ether component of the alkali metal metal salt of sulfosuccinic acid half ester converts monooctyl-monononylphenol and formaldehyde in a 2:1 ratio.
A liquid agrochemical composition according to claim 1, containing a molar ratio of alkylphenol to formaldehyde ranging from 10:9 to 10:9, and 2 to 8 moles of ethylene oxide units per molar equivalent of alkylphenol. 3. The liquid agricultural chemical composition according to claim 1, wherein the mineral montmorillonite is used as the swellable silicate. 4. The liquid agricultural chemical composition according to any one of claims 1 to 3, wherein the active substance or the active substance mixture/hardware is selected from the group consisting of herbicides, fungicides, and insecticides. . 5. The active substance endosulfan as an insecticide, the active substance carpendazim, maneb, mancozep, or fentin hydroxide as an insecticide, and the active substance as a herbicide, diuron, chlortoluron, simazine, and atrazine are used.Claim 4 The liquid agrochemical composition described in Section 1. & Pesticide active substance or active substance mixture 5-60MN%
, alkali metal salt of sulfoconophosphate half ester 0.5
~30% by weight, and 0.5-4% by weight of a mixture of equal parts of an alkali metal salt of lignin sulfonic acid and a swellable alkaline earth metal silicate. The liquid agricultural chemical composition according to any one of Items 1 to 3. 7.Additionally, 0-02% by weight of a swelling polysaccharide, 0-6.0% by weight of a conventional wetting or dispersing agent, 0-10% by weight of an antifreeze agent, 0-8% by weight of an emollient, and 0-2% by weight of a preservative. 7. The liquid agricultural chemical composition according to claim 6, which contains 0.2 to 3 parts by weight of an antifoaming agent. 8. In order to control harmful insects, plants or fungi, an effective amount of an aqueous dilution is applied to these or to plants or soil infested by them. The liquid agricultural chemical composition according to any one of Items 1 to 7.